Polyalkylene polyamine derivatives

ABSTRACT

New polyalkylene polyamine derivatives are preparable by a new process comprising reacting a primary or secondary aliphatic amine which bears a carboxyl, hydroxy or phosphoric acid ester group in the Alpha or Beta position, with an aminoalkylsulphuric acid ester in the presence of an alkali metal hydroxide, and are useful intermediates. Particularly they may be N-acylated and then converted into the corresponding quaternary ammonium compounds which are suitable as auxiliary agents or textile treatment agents.

United States Patent Hochreuter et al. Oct. 7, 1975 [54] POLYALKYLENE POLYAMINE 3,551,461 12/1970 Thayer 260/403 DERIVATIVES [75] Inventors: Richard Hochreuter, Oberwil; Primary Examiner E1be1-t L Roberts P Rabinowitl, Geneva, both of Attorney, Agent, or F irmGerald D. Sharkin; Richard Switzerland E. Vila; Joseph J. Borovian [73] Assignee: Sandoz Ltd., Basle, Switzerland 22 Filed: Ma 31 1973 l 1 y 57 ABSTRACT [21] Appl. No.: 365,606

New polyalkylene polyamine derivatives are prepara- [30] Foreign Application Priority Data ble by a new process comprising reacting a primary or 30 l 972 G 2258614 secondary aliphatic amine which bears a carboxyl, hydroxy or phosphoric acid ester group in the a or B position, with an aminoalkyl-sulphuric acid ester in the [52] 2 2 presence of an alkali metal hydroxide, and are useful 51 I t Cl 2 J /6 intermediates. Particularly they may be N-acylated 266/403 404 5 and then converted into the corresponding quaternary 1 0 care ammonium compounds which are suitable as auxiliary 5 References Cited agents or textile treatment agents.

UNITED STATES PATENTS 6/1960 Shokal 260/563 5 Claims, No Drawings POLYALKYLENE POLYAMINE DERIVATIVES The present invention relates to polyalkylene polyamine derivatives.

The invention provides a process for the production of polyalkylene polyamine derivatives, which comprises reacting a primary or secondary aliphatic amine which bears a carboxyl, hydroxy or phosphoric acid ester group in the a or ,8 position, with an aminoalkylsulphuric acid ester in the presence of an alkali metal hydroxide.

A preferred embodiment of the process is the reaction of an amine of formula 1,

l in which R signifies COOH, CH OH, CH-

OPO H or --CHO1-1R in which R signifies an alkyl group of 1 to 4 carbon atoms, and R signifies hydrogen, an alkyl group of 1 to 4 carbon atoms, -CH COOH or CH CH OH, with (1 to mols of a (2-aminoalkyl)-sulphuric acid ester of formula 11,

in which R and R each independently signifies hydrogen or an alkyl radical of l to 4 carbon atoms in the presence of at least 2x moles of alkali metal hydroxide, to produce a compound of formula III,

in which R to R and x are as defined above.

Suitable amines of formula 1 include 2-hydroxy ethylamine, bis-( Z-hydroxyethyl )-amine, methyl-( 2- hydroxycthyl)-amine, aminoacctic acid, aminodiacetic acid, isopropanolamine and phosphoric acid mono-(2- aminoethyl ester). Suitable esters of formula 11 include sulphuric acid mono-(Z-aminoethylester), sulphuric acid mono-(Z-methylaminoethylester) and sulphuric acid mono-( 2-amino-iso-propylester).

The process of the invention is preferably carried out in aqueous or aqueous-lower alkanolic solution. Preferred alkali metal hydroxides are sodium and potassium hydroxides and mixtures thereof. Suitable reaction temperatures are from 20 to 150C, preferably from 80 to 120C. The number of mols of aminoalkylsulphuric acid ester relative to the starting amine is not critical but it is preferred to use about 3 to 15 mols. The reaction may be carried out at normal pressure, but excess pressure in the case of low boiling point reagents, e.g. when sulphuric acid-(2-amino-iso-propyl-ester) is used, may be used. The reaction times vary according to the reaction conditions, e.g. according to pressure, and are normally in the range from 5 to 100 hours.

The polyalkylene polyamine product may be isolated in conventional manner, e.g. by partial evaportion and the addition of alkanol such as ethanol, after which the product may be converted into anhydrous form by distillation or concentrated.

The polyalkylene polyamines of the invention are useful as intermediates. For example, they may be acylated in conventional manner to give derivatives which are N-substituted by acyl groups. Such acylated derivatives generally have the acyl groups in more regular position than can usually be obtained with other methods of producing polyalkylene polyamine N-acylated compounds.

Formation of the N-acyl derivatives of the polyalkylene polyamines may be carried out in conventional manner, for example by reacting the polyalkylene polyamine with a carboxylic acid, preferably at to 200C with distillation of the water of reaction, or by reacting the polyalkylene polyamine with a carboxylic acid halide, preferably in aqueous or aqueous-organic medium. Suitable carboxylic acids include natural or synthetic fatty acids or their functional derivatives such as the esters, anhydrides or halides, or the perfluorated aliphatic carboxylic acids derived therefrom which have about 4 to 32 carbon atoms, can be employed. Mention may be made of fatty acids, such as butyric, iso-butyric, n-valeric, caproic, n-heptylic, caprylic, pelargonic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, lignoceric, cerotic, oleic, linoleic and linolenic acid, and their functional derivatives; fatty acids with 8 to 22 carbon atoms are preferred, in particular those with 15, 16, 17 or 18 carbon atoms. Suitable perfluorated aliphatic carboxylic acids are those with a chain length of about 5 to 16, in particular 5 to 14, carbon atoms. Their synthesis is known, for example from U.S. Pat. Nos. 2,519,983 and 2,567,001; perfluorated aliphatic carboxylic acids with 7, 8 or 9 carbon atoms are preferred.

The basic condensation products thus formed can be converted into the corresponding quaternary ammonium compounds, which are more highly soluble in water, for example by treatment with one of the commonly used alkylating agents in conventional manner.

The n-acylated derivatives have manifold technical applications. If they contain alkyl radicals having a medium or greater number of carbon atoms they can usually be used as surface-active agents, suitably as auxiliary agents in the textile, leather, paper and plastics industries, where they may serve as wetting agents, softeners or antistatic agents. If they contain perfluorated alkyl radicals they are usually suitable for use as oil repellent and soil repellent finishing agents.

The invention is illustrated by the following Examples, in which the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 In a sulphonation vessel 14 parts (0.2 mols) of aminoacetic acid, 141 parts 1 mol) of sulphuric acid mono-(2-aminoethylester) and 88 parts (2.2 mols) of sodium hydroxide are dissolved in 200 parts of water. The solution is reacted on the oil bath for 43 hours with heating and reflux, by which time a sodium sulphate precipitate fomis. After the addition of 10 parts of decolourizing carbon the solution is filtered free of the precipitate, then the sodium sulphate remaining in solution is precipitated from the filtrate by the addition of 1 litre of ethanol. The solution is evaporated to give 61 parts of the aminoalkylation product in the form of a pale grey, viscous mass.

16 Parts of the reaction product are reacted with 13.5 parts of stearic acid in a sulphonation vessel for 4 hours at 145 to with vacuum. On subsequent cooling the acylation product is obtained as a wax-like mass which in dilute acetic acid, or after quaternation,

for example with 3.7 parts of dimethyl sulphate, forms opalescent solutions in water. These solutions are suitable for application to textiles as softening or antistatic agents.

EXAMPLE 2 In a sulphonation vessel of 2.5 litres capacity 305 parts mols) of monoethanolamine are weighed out and set with 505 parts (5 mols) of sulphuric acid, added dropwise with cooling. The temperature is increased to 1 and in the following 1 /2 hours is raised further to 200 with gradual evacuation. The sulphuric acid mono-( 2-aminoethylester) formed is allowed to cool to 70, on which a solution of 141 parts 1 mol) of aminoethyl phosphate and 480 parts l2 mols) of sodium hydroxide in 800 parts of water is added. The mixture is reacted for 40 hours with heating and reflux, and after cooling the precipitated sodium sulphate is filtered off. The solution is concentrated by distilling 800 parts of water under vacuum. It is then set with 2 liters of ethanol, the remaining sodium sulphate filtered and the solution evaporated to dryness. 378 Parts of the aminoalkylation product are obtained in the form of a pale, viscous mass.

In a sulphonation vessel 5 parts of the polyamine derivative thus obtained are reacted with 6 parts of stearic acid for 3 hours at 155 to 160 with stirring and evacuation. The acylation product is obtained as a solid, wax like mass which is dispersible in dilute sodium hydroxide solution.

EXAMPLE 3 In a sulphonation vessel of 750 milliliters capacity 28.2 parts (0.2 mols) of aminoethyl phosphate, 155 parts of sulphuric acid mono-( 2-methy1aminoethylester) (1 mol) and 96 parts (2.4 mols) of sodium hydroxide are dissolved in 300 milliliters of water. The solution is reacted for 70 hours with heating and reflux. Decolourizing carbon is added, the solution filtered, l 100 parts of ethanol added to the filtrate and this filtered again, Subsequent evaporation yields 79 parts of the aminoalkylation product in the form of a pale brown, semi-solid mass.

10 Parts of the reaction product are condensed with 12.5 parts of stearic acid under conditions similar to those given in Example 2. The resulting acylation product (19.5 parts) is a pale brown, solid mass which dissolves in dilute acetic acid to form opalescent solutions.

EXAMPLE 4 In a sulphonation vessel of 750 milliliters capacity 28.2 parts (0.2 mols) of phosphoric acid mono-(2- aminoethylester), 155 parts (1 mol) of sulphuric acid mono-( 2-amino-iso-propylester and 96 parts (2.4 mols) of sodium hydroxide are dissolved in 200 parts of water and reacted for 70 hours with heating and reflux. Subsequently 10 parts of decolourizing carbon are added and the solution is filtered, the remaining sodium sulphate precipitated from the filtrate by the addition of 1 liter of alcohol, the filtrate filtered again and evaporated. 99 Parts of the aminoalkylation product in the form of a pale brown, semi-solid mass are obtained.

Parts of the polyamine phosphate thus formed are melted with parts of stearic acid in sulphonation vessel, the melt held at 145 to 150 for 4 hours under vacuum and then allowed to cool. the acylation product is obtained in the form of a yellowish wax-like mass which forms clear solutions in a mixture of 2 parts of water and 1 part of ethanol EXAMPLE 5 A sulphonation vessel of 2.5 liters capacity is charged with 305 parts (5 mol) of 2-hydroxyethylamine, to which 505 parts (5 mols) of sulphuric acid are added dropwise with cooling by means of icewater. In 2 hours the temperature is raised to 210 with gradual evaporation to reach 14 mm Torr. After subsequent cooling to 66 a solution of 61 parts (1 mol) of 2- hydroxyethylamine and 400 parts (10 mols) of sodium hydroxide in 800 parts of water, the addition of 1800 parts of ethanol and further filtration to remove the remaining sodium sulphate. The solution is completely evaporated, on which the amino-alkylation product is obtained in the form of a brownish liquid in a yield of 284.5 parts.

In a round-bottom vessel 7 parts of the aminoalkylation product and 10 parts of technical perfluoroctoic acid are reacted for 7 hours at to under vacuum with stirring. 16.6 Parts of the perfluorated acyl derivative are obtained as a soft, viscous mass which is soluble in ethanol.

This product is suitable for the oil and soil repellent finishing of textiles, leather, paper and plastics, A product with similar properties is obtained when the 10 parts of perfluoroctoic acid for acylation are increased to 20 parts and the reaction carried out as described above.

A further aminoalkylation product may be obtained in similar manner to the above if 2- hydroxypropylamine is used in place of the 2- hydroxyethylamine reacted with the sulphuric acid ester.

EXAMPLE 6 In a sulphonation vessel 10 parts of the aminoalkylation product obtained as in Example 2 are mixed with 10 parts of technical peerfluoroctoic acid and heated on an oil bath to 130 to 135 with stirring and gradual evacuation. After reaction for 6 hours abd subsequent cooling, 18.7 parts of the acylation product are obtained in the form of a sticky, yellowish mass. In a mixture of water and ethanol, weight ratio 1:1, the product dissolves to give clear solutions. It is suitable for the same applications as the final product described in Example 5.

A compound with comparably good properties is obtainable by the same operating procedure when the 10 parts of technical perfiuoroctoic acid specified in Example 5 are increased to 10 parts for the acylation reaction.

EXAMPLE 7 8'Parts of the aminoalkylation product according to Example 1 are acylated with 10 parts of technical perfluoroctoic acid as described in Example 6. 17 Parts of the acylation product are obtained as a soft, viscous mass.

This compound is very suitable for the oil, and soil repellent finishing of textiles, paper, leather and plastics.

What is claimed is:

1. A process for producing an N-acylated polyalkylene polyamine derivative which comprises reacting a compound of the formula in which R is COOl-l, CH Ol-l, CH OPO H or CHOHR wherein R is alkyl of 1 to 4 carbon atoms, and R is hydrogen, alkyl of l to 4 carbon atoms,

Cl-l COOH or CH Cl-l Ol-l, with x mols of a compound of the formula 2. A process according to claim 1, wherein aminoethyl phosphate is reacted with sulphuric acid mono- (2-aminoethyl ester) in the presence of sodium hydroxide and the resulting product is condensed with stearic acid.

3. A process according to claim 1 wherein the acylation is effected with a fatty acid of 8 to 22 carbon atoms or a halide, anhydride or ester thereof, or with a perfluorated aliphatic carboxylic acid of 5 to 16 carbon atoms or a halide, anhydride or ester thereof.

4. A process according to claim 3 in which the fatty acid is of l5, l6, l7 or 18 carbon atoms and the perfluorated aliphatic carboxylic acid is of 7, 8 or 9 carbon atoms.

5. A process according to claim 3 wherein the N- acylation is effected at a temperature of to 200C. 

1. A PROCESS FOR PRODUCING AN N-ACYLATED POLYALKYLENE POLYAMINE DERIVATIVE WHICH COMPRISES REACTING A COMPOUND OF THE FORMULA
 2. A process according to claim 1, wherein aminoethyl phosphate is reacted with sulphuric acid mono-(2-aminoethyl ester) in the presence of sodium hydroxide and the resulting product is condensed with stearic acid.
 3. A process according to claim 1 wherein the acylation is effeCted with a fatty acid of 8 to 22 carbon atoms or a halide, anhydride or ester thereof, or with a perfluorated aliphatic carboxylic acid of 5 to 16 carbon atoms or a halide, anhydride or ester thereof.
 4. A process according to claim 3 in which the fatty acid is of 15, 16, 17 or 18 carbon atoms and the perfluorated aliphaatic carboxylic acid is of 7, 8 or 9 carbon atoms.
 5. A process according to claim 3 wherein the N-acylation is effected at a temperature of 120* to 200*C. 